In-situ upgrading of bitumen or heavy oil

ABSTRACT

A method is disclosed for in-situ upgrading bitumen or heavy oils during thermal recovery operations. In one embodiment, steam injection for thermal recovery of bitumen in a dolomitic or limestone reservoir matrix material can be carried out at a higher temperature, a higher pressure, a longer dwell time or a combination of all three to allow the mobilized bitumen to remain in contact with the catalytic materials in the dolomitic or limestone reservoir matrix material for longer times at higher temperatures and pressures. In another embodiment, catalytic materials such as for example, oxides or carbonates of calcium, magnesium, potassium, nickel and/or iron can be injected into the reservoir along with steam to further enhance catalytic activity during the heating, mobilization and recovery phases of a thermal recovery operation.

CROSS REFERENCE TO RELATED APPLICATION

The present application claims the benefits, under 35 U.S.C. §119(e), ofU.S. Provisional Application Ser. No. 61/560,618 entitled “In-SituUpgrading of Bitumen or Heavy Oil” filed Nov. 16, 2011, which isincorporated herein by reference.

FIELD

The present disclosure relates to in-situ upgrading of heavy oils andbitumen in general and to upgrading by naturally occurring or injectedcatalysts in particular.

BACKGROUND

There are an estimated 300 million barrels of recoverable bitumen fromAlberta's Athabasca oil sands. There is an approximately equal amount ofpotentially recoverable bitumen from the carbonates in the GrosmontCarbonates, also in Alberta.

Bitumen does not flow at ambient reservoir temperatures and has an APIdensity of typically less than ˜10. Heavy crude oils also typically donot flow at ambient reservoir temperatures and have API densities in theapproximate range of from ˜10 to ˜20. In order to mobilize thesehydrocarbons so that they can be recovered when they are too deep tomine, thermal methods such as for example Steam Assisted Gravity Drain(“SAGD”), solvent methods such as for example Vapor Extraction (“VAPEX”)and combinations of thermal and solvent methods such as for exampleSolvent Assisted Process “SAP”, Steam Alternating Solvent “SAS” and thelike are used.

SAGD and other thermal methods are usually carried out by injectingsteam into the formation at temperatures typically in the range of 150to 400 C and pressures typically in the range of 1 to 15 MPa. Theseconditions may be maintained in the reservoir for days to months.

In the oil sands such as the Athabasca, the reservoir matrix is formedby weakly cemented sand grains which are primarily quartz. In thecarbonates, the reservoir matrix is formed by dolomites which arecomprised, in part, by calcium and magnesium.

In catalytic coal gasification, the use of catalytics such as calcium,magnesium, potassium, nickel and iron are used to allow coalgasification to proceed more quickly and efficiently at lowertemperatures and pressures. Steam gasification of methane is also knownto be enhanced by catalysts such as sodium and calcium at temperaturesin the range of 700 to 900 C and pressures in the range of 0.1 to 5 MPa.The addition of potassium carbonate in the steam gasification ofbituminous coals is known to reduce the optimum temperature and pressurefrom 980 to 760 C and from 6.7 MPa to 3.35 MPa.

Coal gasification is an upgrading process and there is conjecture thatbitumen and heavy oil can be at least partially upgraded by exposure tocatalysts during thermal recovery operations. If so, then these thermalrecovery processes can be enhanced with little extra effort, resultingin considerable energy savings.

There is an economic benefit to achieving a partial upgrade of bitumenand heavy oil during thermal recovery operations since, once recovered,these hydrocarbons must be upgraded either for transportation to arefinery and/or for upgrading into marketable products at a refinery.

SUMMARY

These and other needs are addressed by the various embodiments andconfigurations of the present disclosure which are directed generally tomeans of upgrading bitumen or heavy oils during thermal recoveryoperations by the use of appropriate catalysts and control of thermalrecovery conditions.

A method can include the steps:

(a) injecting a catalytic material and steam into a bitumen-containingdolomitic or limestone reservoir matrix material to form upgradedbitumen, wherein the catalytic material is an oxide, carbonate, and/orchloride of an alkali and alkaline earth metal; and

(b) recovering the upgraded bitumen.

The catalytic material can be one or more of oxides and/or carbonates ofcalcium, magnesium, potassium, nickel, and/or iron.

A recovered API density of upgraded bitumen can be at least about 125%of an in situ API density of bitumen.

A recovered API density of upgraded bitumen can be from about 2 to about10 API degrees greater than an in situ API density of bitumen.

A method can include the steps of:

(a) fracturing a bitumen-containing dolomotic or limestone reservoirmatrix material to increase a permeability and exposed surface area ofthe matrix material; and injecting steam into the fractured matrixmaterial to form an upgraded bitumen, wherein the matrix materialcomprises a catalytic material having a catalytic effect on bitumen; and

(b) injecting steam into the fractured reservoir matrix material to forman upgraded bitumen.

The fracturing can be performed by one or more of hydro-fracturing,explosive fracturing, and block caving.

The catalytic material can be an alkali and/or alkaline earth metalcarbonate or bicarbonate.

A method can include the steps of:

(a) recovering, by steam injection, bitumen from a bitumen-containingmaterial;

(b) in an underground excavation, contacting the recovered bitumen withexcavated limestone and/or dolomite to upgrade the bitumen; and

(c) recovering the upgraded bitumen.

The excavated limestone and/or dolomite can include a catalytic materialhaving a catalytic effect on bitumen.

The catalytic material can be one or more of an oxide, chloride, and/orcarbonate of an alkali, alkaline earth, and transition metal.

The underground excavation can include an underground working area andan underground chamber containing the excavated limestone and/ordolomite and injector and producer wells for injecting recovered bitumeninto the underground chamber and removing upgraded bitumen from theunderground chamber, respectively.

The excavated limestone and/or dolomite could have been used in carbondioxide scrubbing operations to remove carbon dioxide from refinery fluegas.

A thermal or thermal plus solvent process can be applied to therecovered bitumen in the underground excavation.

The contacting step can be performed by one or more of SAGD, CSS, andsteam flooding.

The catalytic material can be contained within the at least one oflimestone and dolomite.

The catalytic material can be added to the at least one of limestone anddolomite.

A recovered API density of the upgraded bitumen can be at least about125% of an in situ API density of the bitumen, before recovery.

An upgraded API density of the upgraded bitumen can be from about 2 toabout 10 API degrees greater than an in situ API density of bitumen,before recovery.

The e upgraded API density of the upgraded bitumen can range from about10 to about 18 API degrees.

The underground excavation can be heated to a temperature in the rangeof about 150 to about 200 degrees Celsius in the contacting step.

The various methods disclosed herein can increase the API density ofbitumen typically by about 1 to about 20 API degrees, more typically byabout 2 to about 15 degrees, and more typically by about 2 API degreesto about 10 API degrees. For example, a bitumen with an in-situ API ofabout 8 API degrees may be upgraded to a heavy oil with a recovered APIdensity in the range of approximately about 10 API degrees to about 18API degrees. In another example, a heavy oil has a recovered API densitythat is typically at least about 125%, more typically at least about135%, more typically at least about 145%, and even more typically atleast about 150% of an in situ API density of a bitumen prior toupgrading.

In one embodiment, steam injection for thermal recovery of bitumen in adolomitic or limestone reservoir matrix material can be carried out at ahigher temperature, a higher pressure, a longer dwell time or acombination of all three in order to allow the mobilized bitumen toremain in contact with the catalytic materials in the dolomitic orlimestone reservoir matrix material for longer times at highertemperatures and pressures.

In another embodiment, catalytic materials such as for example, oxidesor carbonates of calcium, magnesium, potassium, nickel and/or iron canbe injected into the reservoir along with steam to further enhancecatalytic activity during the heating, mobilization and recovery phasesof a thermal recovery operation.

In another embodiment, methods such as hydro-fracturing, explosivefracturing and the like may be used to increase the permeability andsurface area of the reservoir matrix material so as to enhance thecontact between the catalytic elements in the dolomitic or limestonereservoir matrix material.

In another embodiment applicable to recovery operations conducted from atunnel or a shaft in or below the hydrocarbon reservoir, block cavingmethods and the like may be used to increase the permeability andsurface area of the reservoir matrix material so as to enhance thecontact between the catalytic elements in the dolomitic or limestonereservoir matrix material.

The above-described embodiments and configurations are neither completenor exhaustive. As will be appreciated, other embodiments of thedisclosure are possible utilizing, alone or in combination, one or moreof the features set forth above or described in detail below.

As noted above, the hybrid transmission configurations all utilize aone-way clutch to prevent reverse power flow from the drive train to afree power turbine.

These and other advantages will be apparent from the disclosurescontained herein.

The phrases at least one, one or more, and/or are open-ended expressionsthat are both conjunctive and disjunctive in operation. For example,each of the expressions “at least one of A, B and C”, “at least one ofA, B, or C”, “one or more of A, B, and C”, “one or more of A, B, or C”and “A, B, and/or C” means A alone, B alone, C alone, A and B together,A and C together, B and C together, or A, B and C together.

The following definitions are used herein:

Acid-producing gases as used herein are gases such as carbon dioxide,sulfur dioxide, nitrogen dioxide and the like when combined with waterprovided by steam to form carbonic acid, sulfuric acid, nitric acid andthe like.

A diluent as used herein is a light hydrocarbon that both dilutes andpartially dissolves in heavy hydrocarbons. In a thermal or non-thermalheavy oil or bitumen production method, a solvent liquid or vapor isused to reduce viscosity of the heavy oil. An injected solvent vaporexpands and dilutes the heavy oil by contact. The diluted heavy oil isthen produced via horizontal or vertical producer wells. Diluent andsolvent are often used interchangeably in the production of heavy oiland bitumen.

A mobilized hydrocarbon is a hydrocarbon that has been made flowable bysome means. For example, some heavy oils and bitumen may be mobilized byheating them or mixing them with a diluent to reduce their viscositiesand allow them to flow under the prevailing drive pressure. Most liquidhydrocarbons may be mobilized by increasing the drive pressure on them,for example by water or gas floods, so that they can overcomeinterfacial and/or surface tensions and begin to flow.

Primary production or recovery is the first stage of hydrocarbonproduction, in which natural reservoir energy, such as gasdrive,waterdrive or gravity drainage, displaces hydrocarbons from thereservoir, into the wellbore and up to surface. Production using anartificial lift system, such as a rod pump, an electrical submersiblepump or a gas-lift installation is considered primary recovery.Secondary production or recovery methods frequently involve anartificial-lift system and/or reservoir injection for pressuremaintenance. The purpose of secondary recovery is to maintain reservoirpressure and to displace hydrocarbons toward the wellbore. Tertiaryproduction or recovery is the third stage of hydrocarbon productionduring which sophisticated techniques that alter the original propertiesof the oil are used. Enhanced oil recovery can begin after a secondaryrecovery process or at any time during the productive life of an oilreservoir. Its purpose is not only to restore formation pressure, butalso to improve oil displacement or fluid flow in the reservoir. Thethree major types of enhanced oil recovery operations are chemicalflooding, miscible displacement and thermal recovery.

A producer is a any producer of natural gas, oil, heavy oil, bitumen,peat or coal from a hydrocarbon reservoir.

The following in-situ process acronyms are used herein:

CSS means Cyclic Steam Stimulation. In the CSS process, steam isinjected into the reservoir at rates of the order of 1000 B/d for aperiod of weeks; the well is then allowed to flow back and is laterpumped. In suitable applications, the production of oil is rapid and theprocess is efficient, at least in the early cycles. If the steampressure is high enough to fracture the reservoir and thus allowinjection, it can also be used to produce the very viscous oil of theoil sands at an economic rate. The main drawback of the cyclic steamstimulation process is that it often allows only about 15% to 25% of theoil to be recovered before the oil-to-steam ratio becomes prohibitivelylow.

ESEIEH means Solvent Extraction Incorporating Electromagnetic Heating

HAGD is an acronym for Heat Assisted Gravity Drain. In the US oilshales, one recovery method being implemented in pilot projects involvesthe use of resistance heaters and heating elements to raise thetemperature of the oil shales so that oil is produced. These methods arebeing considered for application to both oil sand and carbonate depositsin Alberta. These methods are designed to heat heavy oil and bitumendeposits to mobilize these hydrocarbons for production. Heating of oilsands by electrodes, often referred to as a form of HAGD. Direct heatingof oil sands by electrically-powered heating elements is another form ofHAGD.

LASER means Liquid Addition to Steam for Enhancing Recovery

LASER-CSS means Liquid Addition to Steam for Enhancing Recovery ofCyclic Steam Stimulation

N-Solv means thermal solvent process

PHARM means Passive Heat Assisted Recovery Methods

SAGD means Steam Assisted Gravity Drain. Typically, SAGD wells or wellpairs are drilled from the earth's surface down to the bottom of the oilsand deposit and then horizontally along the bottom of the deposit andthen used to inject steam and collect mobilized bitumen.

SAGP means Steam Gas Push.

SA-SAGD means Solvent Assisted SAGD

SC-SAGD means Solvent-Cyclic SAGD

ES-SAGD means Expanding Solvent-SAGD

SAP means Solvent Assisted Process

SAS means Steam Alternating Solvent

SAVES means Solvent Assisted Vapour Extraction with Steam

SAVEX means Steam and Vapour Extraction process

SGS means Steam Gas Solvent.

In a steamflooding process, steam is forced continuously into specificinjection wells and oil is driven to separate production wells. Thezones around the injection wells become heated to the saturationtemperature of the steam, and these zones expand toward the productionwells. Oil and water from the condensation of steam are removed from theproducers. With viscous oil there is a considerable tendency for thesteam to override the reservoir, and this tends to limit the downwardpenetration of the heat and hence the recovery. Steamflooding can allowhigher steam injection rates than steam stimulation; this advantageoften offsets the rather lower thermal efficiency.

VAPEX means Vapour Extraction process and is a process which uses adiluent as the fluid injected into the hydrocarbon formation as amobilizing fluid

It is to be understood that a reference to solvent herein is intended toinclude diluent and a reference to diluent herein is intended to includesolvent.

It is to be understood that a reference to oil herein is intended toinclude low API hydrocarbons such as bitumen (API less than about 10degrees) and heavy crude oils (API from about 10 degrees to about 20degrees) as well as higher API hydrocarbons such as medium crude oils(API from about 20 degrees to about 35 degrees) and light crude oils(API higher than about 35 degrees). A reference to bitumen is also takento mean a reference to low API heavy oils.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure may take form in various components andarrangements of components, and in various steps and arrangements ofsteps. The drawings are only for purposes of illustrating the preferredembodiments and are not to be construed as limiting the disclosure. Inthe drawings, like reference numerals refer to like or analogouscomponents throughout the several views.

FIG. 1 is a schematic of a flow process for in-situ upgrading of bitumenor heavy oil.

FIG. 2 is a schematic of an underground recovery operation includingis-situ upgrading.

DETAILED DESCRIPTION In-Situ Upgrading

Known catalysts for steam gasification are oxides and chlorides ofalkali and alkaline-earth metals and transition metals, separately or incombination. For example, sodium chloride and potassium chloride areknown catalysts while the carbonates of sodium and potassium are knownto have higher catalytic activity. Also, oxides of calcium, iron,magnesium and zinc are known to have catalytic effect on steamgasification of coal. Calcium carbonate and magnesium carbonates areknown to occur naturally in dolomitic and limestone formations.

In one embodiment, steam injection for thermal recovery of bitumen in adolomitic or limestone reservoir matrix material can be carried out at ahigher temperature, a higher pressure, a longer dwell time or acombination of all three in order to allow the mobilized bitumen toremain in contact with the catalytic materials in the dolomitic orlimestone reservoir matrix material for longer times at highertemperatures and pressures.

In another embodiment, catalytic materials such as for example, oxidesor carbonates of calcium, magnesium, potassium, nickel and/or iron canbe injected into the reservoir along with steam to further enhancecatalytic activity during the heating, mobilization and recovery phasesof a thermal recovery operation.

In another embodiment, methods such as hydro-fracturing, explosivefracturing and the like may be used to increase the permeability andsurface area of the reservoir matrix material so as to enhance thecontact between the catalytic elements in the dolomitic or limestonereservoir matrix material.

In another embodiment applicable to recovery operations conducted from atunnel or a shaft in or below the hydrocarbon reservoir, block cavingmethods and the like may be used to increase the permeability andsurface area of the reservoir matrix material so as to enhance thecontact between the catalytic elements in the dolomitic or limestonereservoir matrix material.

Formation of an Upgrading Chamber

Much of the Athabasca is underlain by a competent, thick limestonebasement formation. These formations are well-suited to excavatingtunnels or caverns by a variety of well-known methods such as forexample, drill&blast, roadheaders, tunnel boring machines and the like.

The limestone removed from these excavations has many uses in acomprehensive thermal recovery operation in an overlying or near-bybitumen resource, especially after the bitumen has been recovered andde-watered. In the upgrading and refining processes, these uses includebut are not limited to: water purification, removal of sulfur dioxideand carbon dioxide from recovered gases and flue gases from on-site ornear-by refineries, for aggregate in road construction etcetera and forvarious agricultural uses where transportation distances are not togreat.

One of the principal uses for this limestone is to form calcium oxide(quick lime) which can be hydrated to form slaked lime and used toremove carbon dioxide from flue gases. In the production of quick lime,carbon dioxide is generated. This carbon dioxide is “clean”(uncontaminated by sulfur dioxide and NOXs for example) and can bereadily captured for various uses or it can be sold.

When used to remove carbon dioxide from flue gases, a “dirty” limestonesludge is formed (contaminated by sulfur dioxide and NOXs for example).One option is to take this dirty limestone and return it to theunderground excavations previously formed in the aforementionedlimestone formation. In effect, clean carbon dioxide (produced byturning limestone into calcium oxide) which has been captured and hassome value, is exchanged for dirty limestone which can be sequestered inthe underground excavations previously formed in the limestoneformation.

In well-known thermal recovery operations of bitumen, a hot, dirtybitumen/water mixture is recovered. It is possible to effect a partialupgrade of this by storing it in a catalytic matrix. Such a matrix canbe provided by the dirty limestone that has been returned to theunderground excavations previously formed in the limestone formation.

If this is anticipated, then the following method can be envisioned:

-   1. Form an excavation in a competent limestone or dolomite formation    under or near a natural bitumen deposit.-   2. Utilize the excavated limestone or dolomite for a variety of    purposes including usage as gravel and removal of carbon dioxide    from refinery flue gases to provide a source of clean carbon    dioxide.-   3. In the excavation in the competent limestone or dolomite    formation, install injector and producer wells suitable for a    thermal stimulation operation such as SAGD, CSS or steam flooding.-   4. Backfill the excavation in the limestone or dolomite formation    with dirty limestone or dolomite sludge from carbon dioxide    scrubbing operations.-   5. Inject the hot, dirty bitumen/water mixture from a conventional    thermal recovery operation into the excavation that now contains    injector and producer wells and is backfilled with dirty limestone    or dolomite sludge.-   6. Steam the “man-made” reservoir and recover partially upgraded    bitumen.

In effect, a new thermal recovery operation can be applied to thebitumen now in a limestone or dolomite matrix or reservoir. It isexpected that there will be some upgrading of the bitumen as the bitumenis further heated and recovered for a second time.

It is noted that the installation of injector and producer wells will befar less expensive than installation by surface-based horizontaldrilling since they need not be drilled from the surface or even anear-by tunnel or shaft but can be installed directly in an open tunnelor cavern. The cost of recovering the bitumen a second time can be morethan offset by the upgrading action of the bitumen being heated while incontact with the catalytic limestone backfill. This second recoveryoperation is expected to be very efficient because the injector andproducer wells can be installed accurately with optimal separation.Alternately, heating elements or electrodes can be installed to assistor replace heating by steam.

FIG. 1 is a schematic of a flow process for in-situ upgrading of bitumenor heavy oil. A thermal or thermal plus solvent process 102 is appliedto a bitumen or heavy oil reservoir 101. A catalyst 103 may also beinjected to enhance the catalytic reactions occurring during the in-situthermal or thermal plus solvent operations to produce an upgradedbitumen 111 which is recovered. This upgraded bitumen may then becombined with excavated and crushed limestone or dolomite in a cavern104 excavated in the basement limestone or dolomite rock. A secondthermal or thermal plus solvent process 105 is applied to the bitumen orheavy oil in cavern 104. A catalyst 106 may also be injected to enhancethe catalytic reactions occurring during the thermal or thermal plussolvent operation in the cavern to produce a further upgraded bitumen112 which is then recovered and prepared for on-site refining or fortransport to market.

FIG. 2 is a schematic of a possible underground recovery operationincluding is-situ upgrading. A bitumen or heavy oil reservoir formation201 is shown over basement rock 202 and overlain by an overburden layer203. An underground working area 203 has been excavated in the basementrock 202. A number of horizontal well pairs 205 have been installed fromthe underground work space 203 into reservoir 201 with wellheads 206installed for operating well pairs 205. As described above, steam orsteam plus solvent and catalysts can be injected at the well headthrough the injector well of well pair 205. Mobilized bitumen or heavyoil is recovered through the producer well of well pair 205.

Bitumen recovery operations have been demonstrated in this manner by theUnderground Test Facility (“UTF”). The Alberta Oil Sands Technology andResearch Authority (“AOSTRA”), a government organization responsible forfunding research in oil sands, was the key link in the transformationfrom concept to implementation. AOSTRA constructed the Underground TestFacility (UTF)) in the Athabasca Oil Sands, in the 1980's tospecifically test the SAGD hypothesis. Using directional drillingtechniques, the original SAGD wells were drilled upwards and thenhorizontally from a tunnel in the limestone basement rock such as shownin FIG. 2.

As also shown in FIG. 2, another underground chamber 204 is alsoexcavated and serves as an upgrading chamber. The chamber is filled withbitumen or heavy oil recovered from reservoir 201 and mixed withcatalytic material such as limestone and/or dolomite rubble which may ormay not be recovered from the material excavated to form either the workspace 203 or the upgrading chamber 204. As shown in FIG. 2,

Upgrading chamber 204 is separated from working space 203 and connectedby one or more passage ways 207. Passage ways 207 can be blocked of bygates or barriers.

The bitumen or heavy oil recovered and catalytic material can then besteamed and heated up to temperatures in the range of about 150 C toabout 200 C for additional upgrading. It is also possible to incorporatemechanical mixing apparatuses in the upgrading chamber to increase thecatalytic action.

The disclosure has been described with reference to the preferredembodiments. Modifications and alterations will occur to others upon areading and understanding of the preceding detailed description. It isintended that the disclosure be construed as including all suchmodifications and alterations insofar as they come within the scope ofthe appended claims or the equivalents thereof.

A number of variations and modifications of the disclosures can be used.As will be appreciated, it would be possible to provide for somefeatures of the disclosures without providing others. For example, thesame slow fill system can be applied to filling any vehicle powered bygaseous fuels such as CNG, propane, hydrogen etcetera. These slow fillsystems could be located, for example, at malls, parking garages,factory outlets and the like. A similar strategy, which is known, ischarging electric cars overnight. The present disclosure differs in thata slow fill CNG location is based on a central storage and meteringfacility serving a number of fueling posts.

The present disclosure, in various embodiments, includes components,methods, processes, systems and/or apparatus substantially as depictedand described herein, including various embodiments, sub-combinations,and subsets thereof. Those of skill in the art will understand how tomake and use the present disclosure after understanding the presentdisclosure. The present disclosure, in various embodiments, includesproviding devices and processes in the absence of items not depictedand/or described herein or in various embodiments hereof, including inthe absence of such items as may have been used in previous devices orprocesses, for example for improving performance, achieving ease and\orreducing cost of implementation.

The foregoing discussion of the disclosure has been presented forpurposes of illustration and description. The foregoing is not intendedto limit the disclosure to the form or forms disclosed herein. In theforegoing Detailed Description for example, various features of thedisclosure are grouped together in one or more embodiments for thepurpose of streamlining the disclosure. This method of disclosure is notto be interpreted as reflecting an intention that the claimed disclosurerequires more features than are expressly recited in each claim. Rather,as the following claims reflect, inventive aspects lie in less than allfeatures of a single foregoing disclosed embodiment. Thus, the followingclaims are hereby incorporated into this Detailed Description, with eachclaim standing on its own as a separate preferred embodiment of thedisclosure.

Moreover though the description of the disclosure has includeddescription of one or more embodiments and certain variations andmodifications, other variations and modifications are within the scopeof the disclosure, e.g., as may be within the skill and knowledge ofthose in the art, after understanding the present disclosure. It isintended to obtain rights which include alternative embodiments to theextent permitted, including alternate, interchangeable and/or equivalentstructures, functions, ranges or steps to those claimed, whether or notsuch alternate, interchangeable and/or equivalent structures, functions,ranges or steps are disclosed herein, and without intending to publiclydedicate any patentable subject matter.

What is claimed is:
 1. A method, comprising: injecting a catalyticmaterial and steam into a bitumen-containing dolomitic or limestonereservoir matrix material to form upgraded bitumen, wherein thecatalytic material is an oxide, carbonate, and/or chloride of an alkaliand alkaline earth metal; and recovering the upgraded bitumen.
 2. Themethod of claim 1, wherein the catalytic material is one or more ofoxides and/or carbonates of calcium, magnesium, potassium, nickel,and/or iron.
 3. The method of claim 1, wherein a recovered API densityof upgraded bitumen is at least about 125% of an in situ API density ofbitumen.
 4. The method of claim 1, wherein a recovered API density ofupgraded bitumen is from about 2 to about 10 API degrees greater than anin situ API density of bitumen.
 5. A method, comprising: fracturing abitumen-containing dolomotic or limestone reservoir matrix material toincrease a permeability and exposed surface area of the matrix material;and injecting steam into the fractured matrix material to form anupgraded bitumen, wherein the matrix material comprises a catalyticmaterial having a catalytic effect on bitumen; and injecting steam intothe fractured reservoir matrix material to form an upgraded bitumen. 6.The method of claim 5, wherein the fracturing is performed by one ormore of hydro-fracturing, explosive fracturing, and block caving.
 7. Themethod of claim 5, wherein the catalytic material is an alkali and/oralkaline earth metal carbonate or bicarbonate.
 8. A method, comprising:recovering, by steam injection, bitumen from a bitumen-containingmaterial; in an underground excavation, contacting the recovered bitumenwith at least one of excavated limestone and dolomite to upgrade thebitumen; and recovering the upgraded bitumen.
 9. The method of claim 8,wherein the at least one of excavated limestone and dolomite comprises acatalytic material having a catalytic effect on bitumen.
 10. The methodof claim 9, wherein the catalytic material is one or more of an oxide,chloride, and/or carbonate of an alkali, alkaline earth, and transitionmetal.
 11. The method of claim 8, wherein the underground excavationcomprises an underground working area and an underground chambercontaining the at least one of excavated limestone and dolomite andinjector and producer wells for injecting recovered bitumen into theunderground chamber and removing upgraded bitumen from the undergroundchamber, respectively.
 12. The method of claim 8, wherein the at leastone of excavated limestone and dolomite has been used in carbon dioxidescrubbing operations to remove carbon dioxide from refinery flue gas.13. The method of claim 8, wherein a thermal or thermal plus solventprocess is applied to the recovered bitumen in the undergroundexcavation.
 14. The method of claim 8, wherein the contacting step isperformed by one or more of SAGD, CSS, and steam flooding.
 15. Themethod of claim 8, wherein the catalytic material is contained withinthe at least one of limestone and dolomite.
 16. The method of claim 8,wherein the catalytic material is added to the at least one of limestoneand dolomite.
 17. The method of claim 8, wherein a recovered API densityof the upgraded bitumen is at least about 125% of an in situ API densityof the bitumen, before recovery.
 18. The method of claim 8, wherein aupgraded API density of the upgraded bitumen is from about 2 to about 10API degrees greater than an in situ API density of bitumen, beforerecovery.
 19. The method of claim 8, wherein the upgraded API density ofthe upgraded bitumen ranges from about 10 to about 18 API degrees. 20.The method of claim 8, wherein the underground excavation is heated to atemperature in the range of about 150 to about 200 degrees Celsius inthe contacting step.